Method of making architectural coating with interference colors

ABSTRACT

A transparent article for reflecting solar energy comprising a metal oxide film which exhibits color by absorption and interference effects and a highly reflective metal film is disclosed along with a sputtering method for its production.

This is a division of application Ser. No. 682,136, filed Dec. 17, 1984.

BACKGROUND OF THE INVENTION

The present invention relates generally to the art of transparentcoatings and more particularly to multiple layer colored transparentcoatings, especially for use on architectural glass products.

Architectural glass products with metallic and/or metal oxide films aregrowing in importance as energy demands for heating and cooling becomeincreasingly expensive. Coated glass architectural products generallyfall into two categories, solar energy control and high transmittance,low emissivity coated products.

Solar energy control glass products are generally glass substrates,often tinted, coated with a low visible transmittance colored film whichreduces solar energy transmittance through the windows into the buildinginterior, thereby reducing air conditioning costs. These products aremost effective in warm climates and are most often seen in commercialconstruction. In areas where heating costs are of greater concern, andparticularly in residential construction, high transmittance, lowemissivity coatings are desirble in order to allow high transmittance ofvisible light into the interior while reflecting infrared radiation toretain heat inside the building. High transmittance, low emissivitycoatings are typically multiple layer films wherein an infraredreflecting metal such as silver, gold or copper is sandwiched betweenanti-reflective metal oxide layers such as bismuth, indium and/or tinoxides. Solar energy control films, on the other hand, are typicallysingle layer films of one or more of the metals or oxides of metals suchas cobalt, iron, chromium, nickel, copper, etc.

Wet chemical methods for producing metallic films for solar energycontrol are well known from U.S. Pat. Nos. 3,846,152; 4,091,172;3,723,158 and 3,457,138. Pyrolytic methods for producing metal oxidefilms for solar energy control are well known from U.S. Pat. Nos.3,660,061; 3,658,568; 3,978,272 and 4,100,330.

Sputtering technologies for producing high transmittance, low emissivitymultiple layer coatings are disclosed in U.S. Pat. Nos. 4,462,884 andU.S. Pat. No. 4,508,789. Sputtering techniques for producing solarcontrol films are disclosed in U.S. Pat. Nos. 4,512,863 and 4,594,137.

U.S. Pat. No. 4,022,947 to Grubb et al discloses a transparent panelcapable of transmitting a desired portion of visible radiation whilereflecting a large portion of incident solar radiation, and a method ofpreparing same, by sputtering an iron, nickel and chromium alloy toobtain a transparent metal film, and reactively sputtering the same or asimilar alloy in the presence of oxygen to form an oxide film. In onepreferred embodiment, the metal film lies between the substrate and themetal oxide film. In another preferred embodiment, the metal oxide filmlies between the substrate and the metal film.

SUMMARY OF THE INVENTION

The present invention involves a solar energy control film deposited ona substrate such as glass by cathode sputtering, preferably magnetronsputtering. The film comprises a layer of a reflective metal and a layerof a colored metal compound, preferably a metal oxide. The metalliclayer provides brightness and reflectivity while the metal oxide layercan be varied in relative thickness to provide a variety of reflectedcolors by interference effects. In addition, because the metal oxide ofthe present invention exhibits significant absorption at a particularwavelength, a desired color can be produced with a relatively thin filmcompared with metal oxides which exhibit interference effects but nosignificant absorption.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A transparent substrate, preferably glass, is coated by cathodesputtering, preferably magnetron sputtering, to provide a solar energycontrol product. The coating comprises at least one layer of areflective metal, such as gold, copper, aluminum and preferably silver,and at least one layer of a metal compound which can provide color byboth absorption and interference effects at varius relative thicknesses,such as the oxides and/or nitrides of metals such as iron alloys, nickelalloys, copper, iron and cobalt. A preferred metal compound is an oxideof stainless steel.

In a preferred embodiment of the present invention, a glass surface isfirst coated with a layer of stainless steel oxide by sputtering astainless steel cathode target in an oxidizing reactive atmosphere. Thestainless steel oxide coated surface is then further coated with a layerof silver by sputtering a silver cathode target in a nonreactiveatmosphere such as argon. Preferably, a protective coating is depositedover the silver. In a most preferred embodiment of the presentinvention, the protective coating is stainless steel deposited bysputtering a stainless steel cathode target in a nonreactive atmospheresuch as argon. The relative thicknesses of the coating layers can bevaried to yield of reflected colors. While interference colors can beobtained with relatively nonabsorbing materials such as indium oxide ortin oxide, much thicker films are required to produce colors equivalentto those of thinner films of absorbing compounds such as stainless steeloxide. For example, an indium oxide film about 1375 Angstroms thick isrequired to produce a gold color compared to about 300 to 600 Angstromsfor stainless steel oxide. Moreover, the gold reflectance of thestainless steel oxide is more intensely colored due to the absorptanceof the stainless steel oxide in the blue wavelength range of thespectrum.

In a most preferred embodiment, stainless steel oxide, silver andstainless steel layers are combined to produce a rich gold coloredcoating. The present invention will be further understood from thedescriptions of specific examples which follow.

EXAMPLE I

A multiple layer coating of stainless steel oxide and silver with astainless steel protective coating is deposited on a glass substrateunder the following conditions, in one pass under multiple cathodes insequence. A clean glass substrate is maintained in a vacuum chamber inan atmosphere of 50 percent oxygen and 50 percent argon at a pressure of4 microns. With two stainless steel cathodes powered at 43 kilowattseach and a line speed of 100 inches (2.54 meters) per minute, astainless steel oxide coating is deposited at a thickness of 300 to 600Angstroms, decreasing the luminous transmittance of the glass from about90 percent to about 75 percent. Next, a silver cathode is sputtered inan inert argon atmosphere. With the same line speed and a power of 6kilowatts, a silver coating about 200 to 250 Angstroms thick isdeposited over the stainless steel oxide coating, further reducing theluminous transmittance to about 14 percent. Finally, since an exposedsilver film is particularly vulnerable, a very thin protective film isdeposited over the silver by sputtering a stainless steel cathode in aninert argon atmosphere. With the same line speed and minimal power ofabout 1 kilowatt, the stainless steel protective coating is deposited toa thickness of about 10 to 50 Angstroms, resulting in a final luminoustransmittance of about 12 percent. The thickness of the protective layeris minimized in order to minimize the decrease in transmittance as wellas to minimize any decrease in the reflectivity of the silver layer. Thecoated article has a bright gold appearance from the glass sideresulting from both interference effects and absorption properties ofthe stainless steel oxide, which absorbs nearly 30 percent at awavelength of 4000 Angstroms but only about 5 percent at wavelengths of5500 Angstroms and higher. The stainless steel composition used in thisexample is the 316 alloy, which comprises about 68 percent iron, 17percent chromium, 12 percent nickel and 2.25 percent molybdenum. Theluminous reflectance of the coated article is 67.7 percent from thecoated surface and 52.9 percent from the glass side. The reflected colorhas dominant wavelengths of 579 and 576 and excitation purities of 15.2and 42.4 from the coated and glass sides respectively. In a doubleglazed unit, the coated article provides a shading coefficient of 0.17and summer and winter U-values of 0.30.

EXAMPLES II-X

Coated articles reflecting various colors ranging from greenish yellowthrough yellow, yellowish orange, orange, reddish orange and red topurple are prepared by depositing stainless steel oxide, silver andstainless steel as in Example I to various relative thicknesses. Whilethe thicknesses are not measured directly, the transmittances after eachsputtering step are indicative of the individual layer thicknesses. Thevarying thicknesses are obtained by varying the power to the cathodeand/or the number of passes under a cathode. In the following table, thetransmittances are shown after the deposition of the first layer ofstainless steel oxide (SS oxide), after the layer of silver, and afterthe protective layer of stainless steel (SS). The table also includesthe luminous reflectance from the coated side, R₁, and the glass side,R₂.

                  TABLE                                                           ______________________________________                                                                %                                                     % Transmittance         Reflectance                                                                             Color                                       Example                                                                              SS Oxide Silver   SS   R.sub.1                                                                            R.sub.2                                                                            R.sub.2                               ______________________________________                                        II     62.1     45.0     29.4 37.4 9.5  Orange                                III    55.3     40.4     28.7 40.5 6.1  Red                                   IV     51.8     37.3     26.8 43.3 5.8  Purple                                V      58.2     16.1     11.4 62.9 27.6 Yellowish                                                                     Orange                                VI     62.9     17.7     13.0 62.3 34.2 Yellow                                VII    70.0     17.6     13.3 63.6 45.9 Yellow                                VIII   77.8     21.3     12.4 78.9 62.8 Greenish                                                                      Yellow                                IX     77.9     25.8     14.9 53.6 47.2 Greenish                                                                      Yellow                                X      78.3     16.2     14.6 51.5 46.3 Gold                                  ______________________________________                                    

The thinner silver films of Examples II to IV produce high reflectancefrom the coated side, but thicker silver films of Examples V to IX arepreferred to provide high reflectance from the glass side as well.

The above examples are offered only to illustrate the present invention.Various other absorbing metal oxides and nitrides which produceinterference colors, such as oxides or nitrides of nickel alloys,copper, iron and cobalt may be used, along with other highly reflectivemetals such as gold, copper or aluminum. Any suitable transparentprotective layer may be employed. The scope of the present invention isdefined by the following claims.

I claim:
 1. A method of making a solar energy reflecting coated articlecomprising the steps of:a. sputtering onto a surface of a substrate afirst transparent coating of a metal compound which exhibits color byabsorption and interference effects; b. sputtering a highly infraredreflective transparent metallic film on said colored metal compoundcoating; and c. sputtering a transparent protective metal film on saidinfrared reflective metallic film.
 2. A method according to claim 1,wherein said substrate is glass and said sputtering is magneticallyenhanced.
 3. A method according to claim 2, wherein said metal compoundcomprises a metal oxide deposited by sputtering a metal selected fromthe group consisting of stainless steel, nickel alloys, copper, iron,cobalt and mixtures thereof in an oxidizing atmosphere.
 4. A methodaccording to claim 3, wherein stainless steel is sputtered in anoxidizing atmosphere to form a stainless steel oxide film.
 5. A methodaccording to claim 4, wherein said metallic film is deposited bysputtering a metal selected from the group consisting of silver, gold,copper, aluminum and mixtures thereof in an inert atmosphere.
 6. Amethod according to claim 5, wherein silver is sputtered in anatmosphere comprising argon.
 7. A method according to claim 6, wherein atransparent protective metal film is deposited on said silver film.
 8. Amethod according to claim 7, wherein a transparent protective filmcomprising stainless steel is deposited on said silver film.
 9. A methodaccording to claim 8, wherein the protective film is deposited bysputtering stainless steel in an inert atmosphere.
 10. A methodaccording to claim 9, wherein the stainless steel oxide film andstainless steel protective film are both deposited by sputtering ofstainless steel comprising about 68 percent iron, 17 percent chromium,12 percent nickel and 2.25 percent molybdenum.